Web on stampable sheet and method of making

ABSTRACT

Web containing a thermoplastic resin, reinforcing fibers and thermal expandable particles dispersed therein. The thermoplastic resin and the reinforcing fibers are uniformly dispersed in a thickness direction and the thermal expandable particles are eccentrically located toward one-side surface of the web, wherein opposite sides of the web have substantially different specific gravity and density.

CROSS REFERENCE TO RELATED APPLICATION

The instant application is a continuation application of U.S. patentapplication Ser. No. 11/916,894, which is a US National stage of PCTApplication No. PCT/JP2006/311885 filed Jun. 7, 2006, designating theUnited States of America. The disclosures of U.S. application Ser. No.11/916,894 is expressly incorporated by reference herein in theirentireties. The present application also claims priority under 35 U.S.C.§119 of Japanese Patent Application No. 2005-166414 filed on Jun. 7,2005.

TECHNICAL FIELD

The invention relates to a stampable sheet expanded product used as notonly an inner panel member of a vehicle, an engine cover or the like butalso a sound absorbing member, a sound proof wall or the like in a fieldof a building material, a web and a stampable sheet suitable for use inthe production thereof and a method of producing the same.

RELATED ART

The stampable sheet is a composite material consisting of reinforcingfibers such as glass fiber, carbon fiber or the like and a thermoplasticresin, and is a sheet-shaped raw material suitable for shaping alarge-scale member by expanding under heating and pressing. As themethod of producing the stampable sheet, there is known a method whereinthe reinforcing fibers and the thermoplastic resin are dispersed into amedium such as foamy solution formed by adding a surfactant to water soas to include fine bubbles and sheet-making the resulting dispersion orpouring the foamy dispersion onto a paper-making screen to remove thefoam to thereby obtain a non-woven deposit (web) and thereafter heatingand pressing the web and solidifying under cooling (see JP-B-55-009119).

The stampable sheet has a nature that as it is heated, the thermoplasticresin is melted and at the same time, the thickness is returned to theoriginal web thickness before the pressing due to the action of springback inherent to the reinforcing fibers. And, the stampable sheet isheated and expanded and press-formed to form a porous shaped producthaving a proper amount of pores, whereby there can be obtained anexpansion molded product having a high stiffness and an excellent soundabsorbing property (see JP-A-60-179234).

The above expansion molded product is a porous body wherein thereinforcing fibers oriented in a random direction are entangled witheach other and bonded and fixed with the molten solidified thermoplasticresin to form a three-dimensional net-work structure. Since thestiffness of the expanded product is proportional to a product ofelastic modulus and cubed thickness, in order to enhance the stiffness,it is effective to increase the elastic modulus or to thicken thethickness.

For the purpose of increasing the thickness of the expansion moldedproduct, there are a method of increasing a thickness of a web as astarting material, and a method of enhancing an expanding property ofthe web. However, the increase of the web thickness unfavorably bringsabout the increase of the weight. Also, the expanding property of thestampable sheet is dependent upon the action of the spring back in thereinforcing fiber, so that the enhancement of the expanding property islimited.

Now, there is proposed a technique wherein the stampable sheet is mixedwith thermal expandable particles having a property of expanding underheating and then expanded by heating to forcedly increase the thicknessof the sheet (see JP-A-2000-328494, JP-A-H10-072798 andJP-A-H02-045135). As the thermal expandable particles, there aregenerally particles having a core-shell type structure with a diameterof about several dozen μm, in which the core is a liquid hydrocarbon andthe shell is a thermoplastic resin having a gas barrier effect. Whensuch particles are heated, the hydrocarbon is vaporized and expanded,while the thermoplastic resin is softened, whereby the particles areexpanded into spheres having a diameter of about several hundreds μm.

DISCLOSURE OF THE INVENTION

For example, the above patent documents 3 (JP-A-2000-328494) and 4(JP-A-H10-072798) disclose a technique that the reinforcing fibers,thermoplastic resin particles and thermal expandable particles aredispersed into water added with a coagulating agent and a thickeningagent and filtered in the paper making. The above coagulating agent isadded for the purpose of coagulating the thermal expandable particles toprevent the thermal expandable particles from discharging through meshesof a paper-making screen in the paper making. However, the stampablesheet obtained by this technique has a problem that since the thermalexpandable particles are coagulated, if it is heated to form an expandedproduct, only the coagulated portion is largely expanded to make theirregularity on the surface of the expansion molded product larger andhence the surface properties are deteriorated and the density of thecoagulated portion in the thermal expandable particles is lowered todecrease the strength of the expansion molded product.

Further the above patent document 5 (JP-A-H02-045135) discloses atechnique that a web subjected to a needling treatment is immersed intoa solution dispersed with thermal expandable particles to uniformlydisperse the thermal expandable particles into the web. In thistechnique, however, since the web is subjected to the needlingtreatment, there is caused a problem that needle traces also remain inthe expansion molded product and buckling is caused about the needletrace to deteriorate the mechanical strength.

It is, therefore, an object of the invention to propose an expansionmolded product of stampable sheet being light in the weight and havingnot only an excellent sound absorbing property but also excellentsurface properties and mechanical strength, a web and a stampable sheetsuitable for use in the production thereof as well as a method ofproducing the same.

The inventors have made various studies in order to solve the aboveproblems of the conventional techniques. As a result, it has been foundthat the above problems can be solved by properly controlling thedistribution of the thermal expandable particles included in the web ina thickness direction through foam-paper-making process.

That is, the thermal expandable particles are kept at the surfaces ofthe bubbles in the foam-paper-making process, so that the particles areuniformly dispersed in the foamy solution. In the foam-paper makingprocess, the thermal expandable particles can be dispersed withoutcoagulating. As a result, the irregularity due to the coagulation of thethermal expandable particles is hardly caused on the surface of theexpansion molded product. In the foam-paper-making process, thereinforcing fibers having a diameter of several dozen μm and a length ofseveral dozen mm and the thermoplastic resin particles having a diameterof about several hundreds μm can be uniformly dispersed into the webafter the paper making in thickness and width directions. However, incase of the paper making of the foamy solution dispersed with thethermal expandable particles having a diameter of about several dozenμm, it has been confirmed to obtain a web wherein the thermal expandableparticles are eccentrically located toward a side of a paper-makingscreen or a side of removing foam by suction and the thermal expandableparticles are hardly existent at a side opposite thereto. This isconsidered due to the fact that since the particles are small, thethermal expandable particles are eccentrically located toward the sideof the paper-making screen by the suction force for the removal of foam.When the web containing the thermal expandable particles eccentricallylocated toward the one face side is used to prepare a stampable sheet orwhen such a stampable sheet is used to prepare an expansion moldedproduct, the distribution state of the thermal expandable particles inthe web is inherited as it is. As a result, in the finally obtainedexpansion molded product, the face side having substantially no thermalexpandable particles is larger in the specific gravity and higher in thedensity as compared with the face side having a great number of thermalexpandable particles, so that the compression strength becomes higherand the bending strength is improved. Further, the expansion moldedproduct having a high density layer existed at its surface more improvesthe sound absorbing property. The invention is based on the aboveknowledge.

That is, the invention is a web containing a thermoplastic resin,reinforcing fibers and thermal expandable particles dispersed thereinand is characterized in that the thermal expandable particles areeccentrically located toward one-side surface of the web. Preferably,the web is a web produced by a foam-paper-making process(foam-paper-made web).

Also, the invention is a stampable sheet containing reinforcing fibersand thermal expandable particles dispersed into a matrix made of athermoplastic resin and is characterized in that the thermal expandableparticles are eccentrically located toward one-side surface of thestampable sheet. Preferably, the stampable sheet is a stampable sheetobtained by heating, pressing and cooling the foam-paper-made web(foam-paper-made stampable sheet).

Furthermore, the invention is an expansion molded product of a stampablesheet in which reinforcing fibers and expanded thermal expandableparticles are adhered with a thermoplastic resin and dispersed thereinand is characterized in that the expanded thermal expandable particlesare eccentrically located toward one-side surface of the expansionmolded product. Preferably, the expansion molded product of stampablesheet is an expansion molded product of stampable sheet obtained byheating, molding and cooling the foam-paper-made stampable sheet(expansion molded product of foam-paper-made stampable sheet).

In addition, the invention proposes a method of producing a web byuniformly dispersing reinforcing fibers, a thermoplastic resin andthermal expandable particles into a surfactant-containing aqueous mediumincluding fine foams therein to prepare a foamy solution and filteringthe foamy solution, characterized in that the thermal expandableparticles are eccentrically located toward one-side surface of the webby removing foams by suction during the filtering.

And also, the invention is a method of producing a stampable sheet byuniformly dispersing reinforcing fibers, a thermoplastic resin andthermal expandable particles into a surfactant-containing aqueous mediumincluding fine foams therein to prepare a foamy solution, filtering thefoamy solution to form a web, and then beating, pressing and cooling theweb to prepare a stampable sheet in which the reinforcing fibers andthermal expandable particles are dispersed into a matrix made of thethermoplastic resin, characterized in that the thermal expandableparticles are eccentrically located toward one-side surface of thestampable sheet by removing foams by suction during the filtering andeccentrically locating the thermal expandable particles toward one-sidesurface of the web.

Moreover, the invention is a method of producing an expansion moldedproduct of a stampable sheet by uniformly dispersing reinforcing fibers,a thermoplastic resin and thermal expandable particles into asurfactant-containing aqueous medium including fine foams therein toprepare a foamy solution, filtering the foamy solution to form a web,and then heating, pressing and cooling the web to prepare a stampablesheet, and thereafter heating the stampable sheet to expand the thermalexpandable particles and shaping and cooling to prepare an expansionmolded product of the stampable sheet in which the reinforcing fibersand the expanded thermal expandable particles are adhered with thethermoplastic resin and dispersed thereinto, characterized in that theexpanded thermal expandable particles are eccentrically located towardone-side surface of the expansion molded product of the stampable sheetby removing foam by suction during the filtering and eccentricallylocating the thermal expandable particles toward one-side surface of theweb.

According to the invention, the expansion molded product of stampablesheet which is not only light and good in the surface property, but alsogood in the mechanical strength such as the bending strength andrigidity.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a graph showing a comparison of expansion molded products ofstampable sheet on sound absorbing property.

BEST MODE FOR CARRYING OUT THE INVENTION

The invention has a characteristic that in the production of theexpansion molded product of stampable sheet, a web as a startingmaterial is prepared by using a foam-paper-making process so as toeccentrically locate thermal expandable particles included in the web atone-side surface, whereby a porosity at the side containing a greatnumber of the thermal expandable particles is made larger and a porosityat the other side surface containing a few of the thermal expandableparticles is made smaller to increase the density, whereby the expandingproperty as a whole is enhanced but also the mechanical strength andsound absorbing property of the expansion molded product are improvedand the surface property is also improved. The construction of theinvention will be described in detail below.

At first, the structures of the web, stampable sheet and expansionmolded product of stampable sheet (hereinafter also referred to“expansion molded product” simply) according to the invention will bedescribed below.

The web of the invention consists of reinforcing fibers, a thermoplasticresin and thermal expandable particles and is produced by afoam-paper-making process mentioned later and has a structure that thereinforcing fibers and thermoplastic resin are distributed at anapproximately equal ratio in the thickness direction of the web but thethermal expandable particles are eccentrically located at one-sidesurface of the web. That is, the great number of the thermal expandableparticles are existent in the vicinity of the one-side surface of theweb, and the number of the particles is decreased toward the inside ofthe web, and hence the thermal expandable particles are hardly existentin the vicinity of the opposite surface.

The stampable sheet according to the invention, which is obtained byheating, pressing and cooling the above web, has a structure that thematrix is constituted with the thermoplastic resin melted and solidifiedby the heating and cooling and the reinforcing fibers and thermalexpandable particles are dispersed into the matrix. In the stampablesheet according to the invention, the distribution state of the thermalexpandable particles in the web is inherited as it is, so that thethermal expandable particles in the stampable sheet show a distributionthat they are existent in the vicinity of the one-side surface of thesheet and are gradually decreased toward the inside thereof and arehardly existent in the vicinity of the opposite surface.

Similarly, in the expansion molded product obtained by expanding andshaping the above stampable sheet, the distribution state of the thermalexpandable particles in the web is inherited as it is. That is, theexpansion molded product according to the invention has a porousstructure that the reinforcing fibers and the expanded thermalexpandable particles are adhered with each other by the melted andsolidified thermoplastic resin and dispersed thereinto, wherein thegreat number of the thermal expandable particles are existent in thevicinity of the one-side surface of the expansion molded product, andthe number of the particles is decreased toward the inside of theexpansion molded product, and hence the thermal expandable particles arehardly existent in the vicinity of the opposite surface. As a result, inthe expansion molded product of the invention, the side of the surfacehaving less thermal expandable particles is smooth in the surface andlarge in the specific gravity and high in the density as compared withthe side containing the great number of the thermal expandableparticles, so that the mechanical properties such as bending strength,stiffness and the like are improved and also the sound absorbingproperty becomes excellent.

Then, there will be described the reinforcing fiber, thermoplastic resinand thermal expandable particles constituting the web, stampable sheetand expansion molded product according to the invention.

As the reinforcing fibers used in the invention may be used inorganicfibers, organic fibers or a composite or mixed fibers thereof. As thefiber capable of being used may be mentioned inorganic fibers such asglass fiber, carbon fiber, boron fiber, stainless fiber and other metalfiber and mineral fiber; and organic fibers such as aramid fiber,polyester fiber, polyamide fiber, natural fiber of hemp and the like.Also, these fibers may be used alone or in a combination of two or more.Moreover, from a viewpoint that a high reinforcing effect is given tothe expansion molded product, the inorganic fibers are preferable ratherthan the organic fibers, and among them the use of carbon fiber ispreferable in view of the importance on the strength. On the other hand,the glass fiber is preferable in view of the cost, while the organicfibers are preferable from a viewpoint of the thermal recycle thatresidues are not retained even in the burning.

The reinforcing fiber is preferable to have an average diameter of 3-50μmφ from a viewpoint of sufficiently ensuring the reinforcing effect andexpansion property of the stampable sheet. More preferably, the averagediameter is 3-30 μmφ. By using the reinforcing fibers having the aboverange of the average diameter, the yield of the thermal expandableparticles in the machining can be improved. Moreover, if it is expectedto increase the expansion quantity by the synergistic effect of thespring back of the reinforcing fibers and the expansion property of thethermal expandable particles, a mixture of reinforcing fibers having anaverage diameter of 100-1000 μmφ and reinforcing fibers serving to fillin gaps between the fibers and having an average diameter of 3-50 μmφmay be used. Also, the average length of the reinforcing fibers ispreferably a range of 3-100 mm in view that the reinforcing effect,expansion property and shapability are ensured sufficiently.Furthermore, the average length of the reinforcing fibers is morepreferably a range of 3-50 mm from a viewpoint that the thermoplasticresin and the reinforcing fibers are more uniformly dispersed at apre-stage of the step of making the web. Moreover, the above averagediameter and average length are average of values obtained by measuringabout 50 diameters and lengths of reinforcing fibers before using orreinforcing fibers in the web, expansion molded product of stampablesheet with a microscope or the like. Further, the reinforcing fibers maybe observed by means of a microscope or the like after the web,stampable sheet or expansion molded product is fired at a temperature ofabout 600° C.

The reinforcing fibers used in the invention are preferably subjected toa surface treatment with a coupling agent or sizing agent. Particularly,they are preferably subjected to a treatment with a silane couplingagent in order to improve the wettability or adhesiveness between thereinforcing fibers and the thermoplastic resin. As the silane couplingagent, vinylsilane-based, aminosilane-based, epoxysilane-based,methacrylsilane-based, chlorosilane-based, mercaptosilane-based couplingagents and the like may be used. The surface treatment of thereinforcing fibers with the silane coupling agent may be carried out bya well-known method such as a method of spraying a solution of a silanecoupling agent while stirring the reinforcing fibers, a method ofimmersing the reinforcing fibers into a solution of a silane couplingagent, or the like. Moreover, the amount of the silane coupling agenttreated is preferably 0.001-0.3 mass % based on the mass of thereinforcing fibers to be treated. When it is less than 0.001 mass %, theeffect of the silane coupling agent is small and the sufficient adhesionstrength between the reinforcing fibers and the thermoplastic resin isnot obtained, while when it exceeds 0.3 mass %, the effect of the silanecoupling agent is saturated. More preferably, it is a range of 0.005-0.2mass %.

Also, the reinforcing fibers used in the invention are desirablyfibrillated into monofilaments for enhancing the strength and expansionproperty of the stampable sheet. For this end, the reinforcing fibersare preferably treated with water-soluble sizing agent. As the sizingagent, polyethylene oxide-based and polyvinyl alcohol-basedwater-soluble resins and the like may be used. The amount of the greigegoods treated is desirably not more than 2 mass %, preferably not morethan 1 mass % based on the mass of the reinforcing fibers to be treated.When it exceeds 2 mass %, the fibrillation of the fibers in themachining step becomes difficult. Moreover, the lower limit of theamount treated is about 0.05 mass %. When the amount treated is toosmall, the handling property becomes poor.

There will be described the thermoplastic resin used in the inventionbelow.

As the thermoplastic resin used in the invention, for example, apolyolefin resin such as polyethylene, polypropylene or the like;polystyrene, polyvinyl chloride, polyethylene terephthalate,polycarbonate, polyamide, polyacetal and so on, or one or morethermoplastic elastomers such as ethylene-vinyl chloride copolymer,ethylene-vinyl acetate copolymer, styrene-butadiene-acrylonitrilecopolymer, EPM, EPDM and the like may be used. Among them, thepolyolefin resin such as polyethylene, polypropylene or the like ispreferable in a point that the strength, stiffness and shapability areexcellent, and particularly polypropylene is preferable because thebalance of the above properties is excellent and the cost is low.Further, MFR (melt flow rate, at 230° C. and 21.17N) measured underconditions defined in JIS K6921-2:1997 among polypropylene is preferablya range of 1-200 g/10 min., more preferably a range of 10-150 g/10 min.

In order to enhance the adhesiveness of the thermoplastic resin to thereinforcing fibers, non-modified thermoplastic resin may be usedtogether with a thermoplastic resin modified with an acid as unsaturatedcarboxylic acid or unsaturated carboxylic acid anhydride, or variouscompounds such as epoxy compound and so on. The modification treatmentmay be carried out, for example, by graft-copolymerizing polypropylenewith maleic acid, anhydrous maleic acid, acrylic acid or the like. Themodified resin preferably has a modifying group such as acid anhydridegroup, carboxyl group or the like in its molecule from a viewpoint ofthe strength improvement.

As the form of the thermoplastic resin, granular form such as powder,pellet, flake or the like, and fibrous form may be used. It ispreferable to use the fibrous form with the granular form from aviewpoint that the handling property of the web and the yield of thethermal expandable particles are improved and that the meltedthermoplastic resin and the reinforcing fibers are sufficientlyentangled to improve the strength and stiffness in the production of thestampable sheet. In case of using the granular form, it is preferable touse particles having an average particle size of 100-2000 μmφ, and theaverage particle size is more preferably 100-1000 μmφ from a viewpointof uniformly dispersing into the stampable sheet. On the other hand,when the granular form is used together with the fibrous form, it ispreferable to use fibers having an average diameter of 1-50 μmφ and anaverage length of 1-50 mm. The average length is more preferably 1-30 mmfrom a viewpoint of uniformly dispersing in the foamy solution.

Next, there will be described the thermal expandable particles used inthe invention.

The thermal expandable particles used in the invention have a propertythat when they are heated above a certain temperature, the softenedshell expands through a pressure of vaporization expanding core. Theinvention has a great characteristic that the thermal expandableparticles are used as a material constituting the web, expansion moldedproduct of stampable sheet thereof. By using the thermal expandableparticles, a larger expansion amount can be ensured than that in thecase of the spring back of the reinforcing fibers alone, so that thedensity can be more reduced and that the expansion molded product beinglight in the weight and having stiffness can be obtained.

In the invention well-known thermal expandable particles can be used,but particularly preferably core-shell type thermal expandable particlesmay be used in which the core is a liquid hydrocarbon and is enclosedwith a thermoplastic resin having a gas barrier property. Generally, thehydrocarbon used in the core has a boiling point lower than a softeningpoint of the thermoplastic resin as a shell, and may include, forexample, hydrocarbons having a boiling point of not higher than 150° C.such as isobutane, pentane, hexane and the like or ethers. As thethermoplastic resin forming the shell, well-known thermoplastic resins,for example, polyolefin resin such as polyethylene, polypropylene,ethylene-propylene copolymer and the like; polystyrene, polyvinylchloride, polyvinylidene chloride, methacrylic resin, ABS resin,ethylene-vinyl acetate copolymer, polyamide resin, polyethyleneterephthalate, polybutylene terephthalate, polyurethane, polyacetal,polyphenylene sulfide, fluorine resin and the like may be mentioned.Particularly, thermal expandable particles in which the core is made ofa liquid hydrocarbon such as isobutane, pentane, hexane or the like andthe shell is made of a thermoplastic resin such as acrylonitrilecopolymer, polyvinylidene chloride or the like are preferable.

The average diameter of the thermal expandable particles is preferably5-200 μmφ, more preferably not less than 10 μmφ but less than 100 μmφ,further preferably not less than 20 μmφ but less than 100 μmφ before theexpansion under heating. When the particle diameter before the expansionis less than 5 μmφ, the particles pass through the gap between thereinforcing fibers in the machining and are easily dropped off to lowerthe yield. On the other hand, when it exceeds 200 μmφ, the size of thethermal expandable particles after the expansion is too large and hencethe thickness of the expansion molded product becomes non-uniform or thesurface quality is deteriorated. Moreover, the average diameter of thethermal expandable particles after the expansion is preferably 10-2000μmφ, more preferably 20-1000 μmφ. As the average diameter of the thermalexpandable particles after the expansion becomes too small, the amount(number) of the thermal expandable particles required in the expansionof the stampable sheet becomes large. On the other hand, as the averagediameter after the expansion becomes too large, the irregularity isgenerated on the surface of the expansion molded product to deterioratethe surface property. Moreover, the average diameter of the thermalexpandable particles after the expansion is an average of valuesobtained by about 50 diameters of thermal expandable particles in theexpansion molded product by means of an optical microscope or the like.

As mentioned above, when the thermal expandable particles are heatedabove a certain temperature, the softened shell starts the expansionthrough a pressure of vaporization-expanding core. In the invention,such a temperature is called as an “expansion starting temperature” andis defined by a temperature that the particle size of the thermalexpandable particles starts to be rapidly increased when the thermalexpandable particles are heated at 10° C./min. The expansion startingtemperature of the thermal expandable particles used in the invention ispreferably not lower than 120° C., more preferably 130-230° C. When theexpansion starting temperature is lower than 120° C., the heatresistance of the thermal expandable particles themselves is poor andalso it is necessary to extremely lower the drying temperature of themachined web and hence the drying is required to take a long time, whichis not desirable. On the other hand, when the expansion startingtemperature exceeds 230° C., the heating temperature for the expansionis too high and there is a possibility of deteriorating thethermoplastic resin.

The expansion starting temperature of the thermal expandable particlesis preferably small in the difference to the melting point of thethermoplastic resin constituting the matrix. When the expansion startingtemperature of the thermal expandable particles is too lower than themelting point of the thermoplastic resin, the thermoplastic resin ismelted and flown around the reinforcing fibers and hence the thermalexpandable particles are excessively expanded before the adhesion, whichis not desirable. On the other hand, when the expansion startingtemperature is too high, it is required to heat the particles to ahigher temperature for obtaining the sufficient expanded thickness andhence there is a possibility of deteriorating the thermoplastic resin.Therefore, the difference between the expansion starting temperature ofthe thermal expandable particles and the melting point of thethermoplastic resin constituting the matrix is preferably within ±30° C.

Also, in the thermal expandable particles, the maximum expansiontemperature is preferably higher than the melting point of thethermoplastic resin, and the temperature difference thereof ispreferably within 50° C. The maximum expansion temperature used hereinmeans a temperature that the particle size of the thermal expandableparticles becomes maximum when the thermal expandable particles areheated at 10° C./min. If the maximum expansion temperature is higherthan the melting point of the thermoplastic resin, it is necessary toheat the particles to a higher temperature for obtaining the sufficientexpansion property, which causes a fear of deteriorating thethermoplastic resin.

Next, there will be described the weight of the web and the compoundingratio of the reinforcing fibers, thermoplastic resin and thermalexpandable particles constituting the web, stampable sheet and expansionmolded product.

At first, the weight of the web or the like according to the inventionis preferably a range of 100-1000 g/m². When the weight of the web isless than 100 g/m², the sufficient thickness as the expansion moldedproduct is not obtained and also the stiffness lowers, while when itexceeds 1000 g/m², it is difficult to reduce the weight of the expansionmolded product. It is more preferably a range of 100-700 g/m², furtherpreferably 100-500 g/m².

Next, the compounding ratio of the reinforcing fibers to thethermoplastic resin constituting the web or the like according to theinvention differs in accordance with the specific gravities of thereinforcing fiber and thermoplastic resin used and contents of otheradditives and coloring agent, but it is preferable that the reinforcingfibers/thermoplastic resin as a mass ratio is within a range of3/97-60/30 in order to obtain an expansion molded product having highmechanical strengths such as flexural strength (buckling strength),flexural modulus (elastic slope) and the like.

Also, the content of the thermal expandable particles constituting theweb or the like according to the invention is preferably 1-40 parts bymass based on 100 parts by mass of a total of the reinforcing fibers andthermoplastic resin. When the content is less than 1 part by mass, theeffect of improving the expansion property is not developed, while whenit exceeds 40 parts by mass, the effect of improving the expansionproperty becomes too large, which decreases the density in not only theinterior of the expansion molded product but also the surface layer, andlowers the stiffness and buckling resistance.

Moreover, the web or the like according to the invention may containadditives, such as antioxidant, light-resisting stabilizer, metalinactivating agent, flame retardant, carbon black, VOC absorber, VOCdecomposer, deodorant and the like, a coloring agent, an organic binderand so on, if necessary, in addition to the above thermoplastic resin,reinforcing fibers and thermal expandable particles. The additives andcoloring agent may be included by coating onto the reinforcing fibers orthermoplastic resin in advance, or by compounding during the mixing, orby spraying onto the web through a sprayer.

The production method of the web, stampable sheet and expansion moldedproduct according to the invention will be described below.

The production method of the web according to the invention lies in thatthe reinforcing fibers, thermoplastic resin and thermal expandableparticles are dispersed into a surfactant containing aqueous mediumcontaining fine foams as a dispersing solution to prepare a foamysolution and the resulting foamy solution is filtered. If the abovestarting materials are mixed and dispersed in water containing nothickener or coagulating agent instead of the foamy solution, since thespecific gravities of the reinforcing fiber, thermoplastic resin andthermal expandable particle are different from each other, the startingmaterials are separated during the mixing to render into a non-uniformlydispersed state, or thermal expandable particles having a small particlesize pass through the web in the dehydration to lower the yield.Moreover, when the thermal expandable particles are mixed and dispersedin water containing a thickener or a coagulating agent, they areaggregated as previously mentioned. On the contrary, when the foamysolution is used, the reinforcing fibers, thermoplastic resin andthermal expandable particles are maintained at the surface of the foamand uniformly dispersed into the foamy solution, so that the separationis not caused in the transportation of the dispersing solution.

The production of the web according to the invention is carried out bypouring the dispersion (foamy solution) containing the reinforcingfibers, thermoplastic resin and thermal expandable particles in a poroussupport such as a paper-making screen and suctioning from the downsideof the porous support to remove the foam to thereby deposit the solidcontent in the dispersion onto the porous support. When thethermoplastic resin is granular form such as powder pellet or flake, thethermoplastic resin and thermal expandable particles are filteredthrough the filter effect of the reinforcing fibers and hence theyretain in the web. At this moment, the particle size of the thermalexpandable particles is smaller than that of the thermoplastic resin, sothat the thermal expandable particles are easily eccentrically locatedtoward the side of the porous support. That is, there is obtained a webwherein a great number of the thermal expandable particles are existentin the vicinity of the surface of the porous support and the number ofthe thermal expandable particles decreases from the surface toward theinterior and finally the thermal expandable particles are notsubstantially existent in the vicinity of the surface of the oppositeside.

As the surfactant used in the foam-paper-making process any of anionic,nonionic and cationic ones may be used. Particularly, sodiumdodecylbenzene sulfonate, coconut oil fatty acid diethanol amine and thelike are preferably used in view of an excellent effect that thestarting material consisting of the reinforcing fibers and thermoplasticresin is uniformly dispersed into the medium.

The web obtained by the above foam-paper-making is dried under acondition that the thermal expandable particles are not expanded atmaximum (temperature and time). That is, if the thermal expandableparticles in the web are expanded at maximum at the drying stage, thehandling property of the web is deteriorated but also the thermalexpandable particles are collapsed under compression in the productionof the stampable sheet, and there is a case that the expansion propertyof the stampable sheet is insufficient in the subsequent production ofthe expansion molded product.

In order to expand the thermal expandable particles at maximum, acertain heat quantity is required. Therefore, in order that the thermalexpandable particles are not expanded at maximum, it is required tocontrol the heating temperature and time so that the heat quantitycharged in the drying is less than the above certain heat quantity.Concretely, the heating temperature for the drying is not higher than30° C. from the maximum expansion temperature, and the heating time ispreferably within {2×(maximum expansion temperature−expansion starttemperature)} when the heating temperature is not higher than themaximum expansion temperature, while the heating time is preferablywithin {300/(heating temperature−maximum expansion temperature)} and{2×(maximum expansion temperature−expansion start temperature)} when theheating temperature is higher than the maximum expansion temperature.

Moreover, when an emulsion or aqueous solution containing an organicbinder is immersed in the foam-paper made web by applying throughspraying or a roll coater and suctioning from an opposite face sideunder vacuum, the reinforcing fibers, thermoplastic resin and thermalexpandable particles are efficiently adhered to the web in the drying,so that the yield is improved but also the handling property is improvedand the production efficiency is also improved.

Next, the production method of the stampable sheet according to theinvention will be described.

The stampable sheet according to the invention is produced by heatingthe web obtained through the above foam paper making at a temperaturehigher than the softening point or melting point of the thermoplasticresin and under a condition that the thermal expandable particles arenot expanded at maximum (temperature and time), pressurizing, coolingand solidifying, whereby the thermoplastic resin is melted to form asmatrix and the dispersed reinforcing fibers and thermal expandableparticles are sufficiently adhered and bonded through the melted andsolidified thermoplastic resin. The term “condition not causing themaximum expansion (temperature and time)” used herein is the same as inthe aforementioned condition. The reason why the temperature is higherthan the melting point of the thermoplastic resin is due to the factthat when it is lower than the melting point, the thermoplastic resin isnot sufficiently fused to the reinforcing fibers and thermal expandingparticles and hence the required strength is not obtained, while thereason why the thermal expandable particles are heated under thecondition causing no maximum expansion is due to the fact that if thethermal expandable particles are expanded at maximum at the heatingstep, the handling property of the stampable sheet is lowered but alsothe thermal expandable particles are collapsed under compression in theproduction of the stampable sheet and there could be a case that theexpansion property required for the subsequent production of theexpansion molded product is not obtained.

As the pressing condition when the web is heated to melt thethermoplastic resin and pressed to produce the stampable sheet, it ispreferable to compress the web so as to render the specific gravity ofthe stampable sheet into not less than 0.3. When it is less than 0.3,the fluidity of the thermoplastic resin is insufficient and thestructure of dispersing the reinforcing fibers and thermal expandableparticles into the thermoplastic resin as a matrix may not be formed.More preferably, the specific gravity is not less than 0.4. However, asthe web is extremely compressed, there is a possibility that thereinforcing fibers are broken or the sheet weight is decreased (thesheet area becomes large to thin the thickness), so that it ispreferable to conduct the compression at a pressure that the porosity isnot more than zero.

In the production method of the stampable sheet according to theinvention, the pressing of the web may be conducted after the melting ofthe thermoplastic resin or the heating and the pressing may be conductedsimultaneously. As the pressing method, there are an intermittentpressing method of batch system, a continuous pressing method using abelt of teflon or steel, a roll pressing method and the like, and any ofthem may be used. In order to improve the handling property of thestampable sheet, the pressing is carried out during the melting of thethermoplastic resin, and thereafter the pressure is removed to conductthe expansion, and the cooling may be conducted at a state of thicknessthicker than that in the pressing. Further, there is a method whereinthe drying and heating of the web are simultaneously carried out andsubsequently the pressing is conducted, which is economical and good inthe production efficiency.

The production method of the expansion molded product according to theinvention will be described below.

The expansion molded product according to the invention is produced byheating the thus produced stampable sheet above the softeningtemperature or melting point of the thermoplastic resin and theexpansion start temperature of the thermal expandable particles tosoften or melt the thermoplastic resin and at the same time expand thethermal expandable particles and thereafter placing the expanded sheetin a mold and closing the mold and adjusting a clearance of the mold toconduct the shaping and then cooling and solidifying the sheet.

The specific gravity of the expansion molded product is preferably notless than 0.03 but not more than 0.2 as a whole. When the specificgravity is less than 0.03, there could be a case that the bucklingresistance of the expansion molded product is deteriorated, while whenit exceeds 0.2, it is required to increase the thickness for obtainingthe required stiffness and there could be a case that the weightreduction may not be attained. Also, in addition that the specificgravity of the expansion molded product according to the invention isnot more than 0.2 as a whole, it is preferable to form an outerperipheral portion having a specific gravity of more than 0.2 therearound. Since the outer peripheral portion having a specific gravity ofnot less than 0.2 is formed, the dropout of the thermal expandableparticles can be prevented but also the tear strength is improved andhence the whole of the product is hardly folded.

Furthermore, when the expanded sheet is supplied into the mold, asurface skin material having a good design is laminated to a side of aface holding almost none of thermal expandable particles and adheredthereto together with the expansion shaping, whereby there can beobtained the expansion molded product attached with the surface skinaccording to the invention.

In order to improve the strength characteristics such as bucklingresistance, stiffness and the like, and sound absorption property of theexpansion molded product further according to the invention, a highdensity resin layer may be formed on at least one surface of theexpansion molded product. The high density resin layer means a resinlayer having a porosity smaller than that in an inner layer portion ofthe expansion molded product or having no pore.

As the method of forming the high density resin layer, theconventionally known techniques may be used. For example, a methodwherein a solution containing a resin for the formation of the highdensity resin layer is impregnated into at least one surface of the web,stampable sheet or expansion molded product, a method wherein a meltedhigh density resin is extruded in the form of a sheet and laminated, amethod wherein a high density resin sheet is laminated and so on arepreferable. Among them, the method of laminating the resin sheet ispreferable because the lamination is easy for any of the web, stampablesheet and expansion molded product. The thickness of the resin sheet ispreferably not more than 200 μm, more preferably 20-150 μm forsuppressing the increase of the weight. Here, the resin sheet may be asheet made of polypropylene, nylon or linear polyethylene, or amultilayer film formed by laminating two or more of such sheets. Also,the above sheet may be provided with through-holes formed by needlepunching, slits or the like for providing the sound absorption property.

Example 1

As a dispersion, to 1.5 liter of water is added 0.5 g/l of sodiumdodecylbenzene sulfonate as a surfactant, which is stirred to prepare afoamy solution containing fine bubbles, and into the resulting foamysolution are charged reinforcing fibers (carbon fibers, averagediameter: 7 μm, average length: 13 μm) and thermoplastic resin (granularpolypropylene, average particle size: 300 μmφ) shown in Table 1 at acompounding ratio by dry mass shown in Table 2, and further thermalexpandable particles are charged and stirred and dispersed for 10minutes. Then, the foamy solution is poured into a paper machine,vacuumed and removed the foam to prepare a web having a total weight ofreinforcing fibers and thermoplastic resin of 400 g/m² and a weight ofthermal expandable particles of 30 g/m² (foam-paper-made web). Moreover,a porous support having an opening hole of 0.1×0.2 mm is used in themachining.

As the section of the web is observed by means of a microscope, thereinforcing fibers and thermoplastic resin and thermal expandableparticles are dispersed, while a great number of the thermal expandableparticles are existent in the vicinity of the web surface located at theside of the porous support and decrease toward the inside of the web andthe thermal expandable particle is hardly existent in the web surfaceopposite to the side of the porous support.

Then, the thus prepared web is dried at a temperature of 120° C. for 90minutes and placed between press boards of 180° C. and pressed under apressure of 0.1 MPa for 2 minutes so as not to expand the thermalexpandable particles at maximum. In this case, a clearance between thepress boards is 1 mm and the web is compressed to a specific gravity of0.43. Subsequently, the heated and pressed web is placed between coolingboards and cooled at a clearance between the cooling boards of 3 mm toprepare a stampable sheet (foam-paper-made stampable sheet).

As the section of the stampable sheet is observed by means of amicroscope, it shows a structure that the reinforcing fibers and thermalexpandable particles are dispersed in the matrix made of thethermoplastic resin, but the thermal expandable particles aresubstantially existent in the vicinity of the surface located at theside of the porous support and gradually decrease toward the insidethereof and are hardly existent in the vicinity of the surface locatedat the opposite side likewise the web.

Next, the stampable sheet is heated to 190° C. in a far-infrared oven tomelt the thermoplastic resin (polypropylene) and expand the thermalexpandable particles, and thereafter placed on a mold set to a clearanceof 5 mm and compressed and cooled to prepare an expansion moldedproduct.

As the section of the expansion molded product is observed by means of amicroscope, it shows a structure that the reinforcing fibers andexpanded thermal expandable particles are adhered and dispersed with thethermoplastic resin, but the thermal expandable particles aresubstantially existent in the vicinity of the surface of the expansionmolded product located at the side of the porous support and graduallydecrease toward the inside thereof and are hardly existent in thevicinity of the surface located at the opposite side likewise the weband stampable sheet.

Separately, the stampable sheet is heated to a temperature of 190° C. ina far-infrared oven and expanded at a non-restrain state and cooled inair to prepare an expanded sheet, and as the both surfaces of theexpanded sheet are observed, both the surfaces have no irregularity andare smooth. The thickness of the expanded sheet is 10.4 mm.

Then, a test piece having a length of 150 mm and a width of 50 mm istaken out from the expansion molded product and subjected to athree-point flexural test at a span of 100 mm and a crosshead speed of50 mm/min under a load applied to a side of face having small thermalexpandable particles or a side of a high density face to measure amaximum load until buckling and an elastic slope determined from aninitial gradient of a load-displacement curve.

Further, the measurement of an absorption ratio of vertically incidentsound at a state of a back air layer of 0 mm is carried out byvertically incoming a sound wave to a side of a face having smallthermal expandable particles or a side of a high density face accordingto JIS A1405:1998.

TABLE 1 Term Reinforcing fibers Thermoplastic resin Thermal expandableparticles Component carbon fiber (PAN base) polypropylene core portion:hydrocarbon shell portion: acrylonitrile copolymer Shape fibrousGranular fibrous granular Size average diameter: 7 μmφ average particlesize: 300 average diameter: 17 μmφ average particle size: 70 μmφ averagelength: 13 mm or 40 μmφ average length: 20 mm mm Physical property —melting point: 165° C. melting point: 165° C. expansion starting MFR:120 g/10 min. temperature: 155° C. maximum expansion temperature: 175°C. Maker Toho Tenax Co., Ltd. Sumitomo Chemical Industry Daiwabou Co.,ltd. Kureha Co., Ltd. Co., Ltd.

TABLE 2 Production conditions Materials of web of stampable sheetReinforcing Thermal Film laminated Web Clearance fibers and expandableWeb drying on web surface heating of heating thermoplastic Compoundingparticles temperature (high-density temperature press Example resinratio (mass %) (g/m²) (° C.) resin layer) (° C.) (mm) 1 carbon fiber 2530 120 — 180 1.0 granular 75 polypropylene 2 carbon fiber 25 30 120PP40/PA25 180 1.2 granular 75 LLDPE50/PP40 polypropylene 3 carbon fiber25 30 120 PP40/PA25 180 1.2 granular 75 LLDPE50/PP40 polypropylene 4carbon fiber 25 30 120 — 180 1.0 granular 75 polypropylene 5 carbonfiber 40 30 120 PP40/PA25 180 1.2 fibrous 60 LLDPE50/PP40 polypropyleneProperties of expanded sheet expanded at non- Properties of expansionrestraint state molded product Expanded Elastic thickness SurfaceThickness Maximum slope Example (mm) property (mm) load (N) (N/cm)Remarks 1 10.4 both 5.0 12 51 Invention smooth surfaces 2 10.6 both 6.018 67 Invention smooth surfaces 3 — — 8.0 17 70 Invention 4 9.2 both 5.06 30 Comparative irregular surfaces 5 4.8 presence 4.8 4 21 Comparativeof needle traces

Example 2

The web prepared in Example 1 is heated at 180° C. for 5 minutes so asnot to expand the thermal expandable particles at maximum to therebymelt the thermoplastic resin, and thereafter a polypropylene/nylontwo-layer film (polypropylene (PP): thickness 40 μm, melting point 165°C., MFR 8 g/10 min, nylon (PA): thickness 25 μm, melting point 220° C.)is laminated onto a side of a face of the porous support in the web soas to face the polypropylene to the web side and a linearpolyethylene/polypropylene two-layer film having holes of 1 mmφ indiameter formed at 5 holes/cm² by needle punching over a full face(linear polyethylene (LLDPE): thickness 50 μm, melting point 120° C.,MFR 8 g/10 min., polypropylene: thickness 40 μm, melting point 165° C.,MFR 8 g/10 min.) is laminated onto the other face of the web so as toface the polypropylene to the web side, and then they are compressed bypassing between rolls having a clearance of 1.2 mm to prepare astampable sheet having a specific gravity of 0.36. Moreover, MFR of PPis a value measured under conditions of 230° C. and 21.17 N according toJIS K6921-2:1997, and MFR of LLDPE is a value measured under conditionsof 190° C. and 21.17 N according to JIS K6922-2:1997.

As the section of the stampable sheet is observed by means of amicroscope, the (high density) resin layers are existent on bothsurfaces of the stampable sheet and the interior of the resin layer hasa structure that the reinforcing fibers and thermal expandable particlesare dispersed into the matrix made of the thermoplastic resin, but thethermal expandable particles are substantially existent at the side ofthe porous support and are hardly existent at the opposite side.

Also, the stampable sheet is heated to 190° C. in a far-infrared ovenand expanded at a non-restraint state and cooled in air to prepare anexpanded sheet, and hence both surfaces of the expanded sheet have noirregularity and are smooth. The thickness of the expanded sheet is 10.6mm.

Then, the thus obtained stampable sheet is heated to 190° C. in afar-infrared oven and formed in a mold set to a clearance of 6 mm toobtain an expansion molded product.

As the section of the expansion molded product is observed by means of amicroscope, the (high density) resin layers are existent on bothsurfaces of the expansion molded product and the interior of the resinlayer has a structure that the reinforcing fibers and the expandedthermal expandable particles are dispersed into the matrix made of thethermoplastic resin, but the thermal expandable particles aresubstantially existent at the side of the porous support and are hardlyexistent at the opposite side.

With respect to the expansion molded product, the three-point flecuraltest and the measurement of absorption ratio of vertically incidentsound are carried out in the same manner as in Example 1.

Example 3

The stampable sheet prepared in Example 2 is heated to 190° C. andexpanded in a far-infrared oven and further a polyester non-woven fabric(weight: 200 g/m², thickness: 2 mm) as a surface skin is laminated ontoa side of a face laminated with the linear polyethylene (LLDPE) film(side opposite to the porous support), and thereafter the expansionmolding is carried out in a mold set to a clearance of 8 mm to obtain anexpansion molded product provided with the surface skin.

As the surface skin is peeled off from the expansion molded product byhand, the breakage is caused at the surface skin portion and it has beenconfirmed that the surface skin is adhered sufficiently.

As the section of the expansion molded product is observed by means of amicroscope, the (high density) resin layer is existent on the surface ofthe expansion molded product located at the side of the porous supportand the surface skin layer and the (high density) resin layer areexistent at the opposite surface side and the interior of the resinlayer has a structure that the reinforcing fibers and the expandedthermal expandable particles are dispersed into the matrix made of thethermoplastic resin, but the thermal expandable particles aresubstantially existent at the side of the porous support and are hardlyexistent at the opposite side.

With respect to the expansion molded product, the three-point flexuraltest and the measurement of absorption ratio of vertically incidentsound are further carried out in the same manner as in Example 1.

Example 4

As a comparative example, instead of the foamy solution used in Example1, an aqueous solution containing no fine bubble obtained by adding 10 gof 0.5 mass % polyacrylamide as a coagulating agent and 0.05 g ofxthansan gum as a thickener to 1.5 liter of water is used as adispersion, and carbon fibers and polypropylene are charged into thedispersion at a compounding ratio shown in Table 2 and further thermalexpandable particles are charged, from which a web having a total weightof 400 g/m² and a weight of thermal expandable particles of 30 g/m² isprepared in the same manner as in Example 1.

As the section of the web is observed by means of a microscope, thereinforcing fibers are dispersed uniformly, but the thermal expandableparticles are aggregated to form flocks and these flocks are uniformlydispersed in the thickness direction.

Next, a stampable sheet and an expansion molded product are prepared byusing the web in the same manner as in Example 1, and the three-pointflexural test and measurement of absorption ratio of vertically incidentsound are carried out in the same manner as in Example 1.

Also, as the sections of the stampable sheet and the expansion moldedproduct are observed by means of a microscope, the thermal expandableparticles are aggregated to form flocks and these flocks are uniformlydispersed in the thickness direction likewise the web.

Furthermore, the stampable sheet is heated to 190° C. in a far-infraredoven, expanded at a non-restraint state and cooled in air to prepare anexpanded sheet. Both surfaces of the expanded sheets are large in theirregularity because the thermal expandable particles are aggregated.Also, the thickness of the expanded sheet is only 9.2.mm.

Example 5

As a comparative example, reinforcing fibers (carbon fibers, averagediameter 7 μm, average length 40 mm) and thermoplastic resin (fibrouspolypropylene, average diameter 17 μm, average length 20 mm) aresupplied to a card machine at a compounding ratio shown in Table 2,fibrillated and mixed and thereafter subjected to needling of 20points/cm² with a needle punching machine (felt needle No. 25) toprepare a web of 400 g/m², and a sample of 300×300 mm is taken out fromthe web.

Then, the above web sample is immersed in a solution having a solidconcentration of acrylstyrene emulsion of 1 mass % and containing 20mass % of thermal expandable particles and compressed through rolls touniformly impregnate the thermal expandable particles into the interiorthereof to thereby adjust 2.7 g of the thermal expandable particles toremain thereof. The web is dried at 120° C. to obtain a web comprising160 g/m² of carbon fibers, 240 g/m² of fibrous polypropylene and 30 g/m²of thermal expandable particles.

As the section of the web is observed by means of a microscope, thecarbon fibers, fibrous polypropylene and thermal expandable particlesare uniformly dispersed in the thickness direction.

Then, the web is heated at 180° C. for 5 minutes to melt polypropylene,and thereafter a polypropylene/nylon two-layer film (polypropylene (PP):thickness 40 μm, melting point 165° C., MFR 8 g/10 min., nylon (PA):thickness 25 μm, melting point 220° C.) is laminated onto one-side faceof the web so as to face the polypropylene to the web side and a linearpolyethylene/polypropylene two-layer film having holes of 1=0 indiameter formed at 5 holes/cm² by needle punching over a full face(linear polyethylene (LLDPE): thickness 50 μm, melting point 120° C.,MFR 8 g/10 min., polypropylene: thickness 40 μm, melting point 165° C.,MFR 8 g/10 min.) is laminated onto the other face of the web so as toface the polypropylene to the web side in the same manner as in Example2, and then they are compressed by passing between rolls having aclearance of 1.2 mm to prepare a stampable sheet having a specificgravity of 0.36.

Thereafter, the stampable sheet is heated to 190° C. in a far-infraredoven and then the expansion shaping is carried out by using a moldhaving a clearance of 6 mm. In the stampable sheet, however, the carbonfibers are strongly entangled with each other, so that the expansionamount is small and only the expansion molded product of 4.8 mm isobtained.

As the sections of the stampable sheet and the expansion molded productare observed by means of a microscope, the reinforcing fibers andthermal expandable particles are uniformly dispersed in the thicknessdirection.

Also, needle traces by needle punching are retained at the surface ofthe expansion molded product.

With respect to the expansion molded product, the three-point flexuraltest and the measurement of absorption ratio of vertically incidentsound are further carried out in the same manner as in Example 1.

The results of the three-point flexural test on Examples 1-5 are alsoshown in Table 2. As seen from these results, a high value is obtainedin all of the maximum load and elastic slope of the invention examples(Examples 1-3). On the contrary, the sufficient flexural strength andstiffness can not be obtained in the comparative example of Example 4wherein the thermal expandable particles are aggregated and uniformlydistributed and the comparative example of Example 5 wherein the thermalexpandable particles are uniformly distributed and the needle traces areretained at the surface of the expansion molded product.

Also, the results measured on the absorption ratio of verticallyincident sound in Examples 1-5 are shown in FIG. 1. From FIG. 1, it isunderstood that the expansion molded products according to the inventioncontaining the thermal expandable particles eccentrically located towardthe one-side face and having a high density layer at the surface thereof(Examples 1-3) are superior in the sound absorbing property to theexpansion molded products of the comparative examples containing thermalexpandable particles uniformly distributed and having no high densitylayer at the surface thereof (Examples 4, 5).

INDUSTRIAL APPLICABILITY

The expansion molded product according to the invention is light in theweight and excellent in the sound absorbing property and also excellentin the mechanical strength and surface property, so that it can beapplied to not only the field of automobiles and building material butalso the filed of household electrical goods.

The invention claimed is:
 1. A web containing a thermoplastic resin,reinforcing fibers and thermal expandable particles dispersed therein,characterized in that the thermoplastic resin and the reinforcing fibersextending across an entire thickness of the web and are uniformlydispersed in a thickness direction and the thermal expandable particlesare eccentrically located toward one-side surface of the web, whereinopposite sides of the web have substantially different specific gravityand density.
 2. A stampable sheet comprising a single-layer havingreinforcing fibers and thermal expandable particles dispersed into amatrix made of a thermoplastic resin, characterized in that thethermoplastic resin and the reinforcing fibers are uniformly dispersedin a thickness direction of the single-layer and the thermal expandableparticles are eccentrically located toward one-side surface of thesingle-layer, wherein the one-side surface of the single-layer is lowerin density and higher in porosity than an opposite-side surface of thesingle-layer.
 3. A single-layer web containing a thermoplastic resin,reinforcing fibers and thermal expandable particles dispersed therein,wherein the thermoplastic resin and the reinforcing fibers are uniformlydispersed in a thickness direction and the thermal expandable particlesare eccentrically located toward one-side surface of the single-layerweb, wherein opposite sides of the single-layer web have substantiallydifferent specific gravity and density.
 4. A one-layer stampable sheetcomprising reinforcing fibers and thermal expandable particles dispersedinto a matrix made of a thermoplastic resin, wherein the thermoplasticresin and the reinforcing fibers are uniformly dispersed in a thicknessdirection of the one-layer stampable sheet and the thermal expandableparticles are eccentrically located toward one-side surface of theone-layer stampable sheet, wherein the one-side surface of the one-layerstampable sheet is lower in density and higher in porosity than anopposite-side surface of the one-layer stampable sheet.
 5. A web havinga single layer of matrix material containing thermoplastic resin,reinforcing fibers and thermal expandable particles dispersed therein,wherein the thermoplastic resin and the reinforcing fibers are uniformlydispersed in a thickness direction of the matrix material and thethermal expandable particles are eccentrically located toward one-sidesurface of the matrix material, wherein opposite sides of the matrixmaterial have substantially different specific gravity and density.
 6. Astampable sheet having a single layer of matrix material containingreinforcing fibers and thermal expandable particles dispersed in athermoplastic resin, wherein the thermoplastic resin and the reinforcingfibers are uniformly dispersed in the matrix material along a thicknessdirection of the matrix material and the thermal expandable particlesare eccentrically located toward one-side surface of the matrixmaterial, wherein the one-side surface of the matrix material is lowerin density and higher in porosity than an opposite-side surface of thematrix material.